Effect of Temperature on Shear‐Induced Anisotropic Structure in Polymer Clay Hydrogels

Summary: Shear‐induced orientation of nanoparticles in poly(ethylene oxide)/Laponite RD hydrogels has been investigated by small angle neutron scattering (SANS). As temperature is reduced, anisotropy develops at lower shear rates. The two‐correlation length Debye–Anderson–Brumberger (DAB) model provides a good fit to the experimental data. The deduced short‐range correlation length (≈5 nm) is observed to increase with shear. The long‐range correlation length (≈50 nm) shows a strong directional dependence, and decreases when shear is applied. The relative contribution of long‐range order to the SANS intensity is observed to increase with shear and decrease with temperature.

SANS anisotropy |(I_y − I_x)/(I_y + I_x)| as a function of shear rate and q at 2 °C.     

Löslichkeit und Adsorbierbarkeit von Benzoesäure und Salizylsäure in Gegenwart gemischter organischer Lösungsmittel

Ohne Zusammenfassung     

Computation Models for Parameterized Complexity

A parameterized computational problem is a set of pairs (x, k), where k is a distinguished item called “parameter”. FPT is the class of fixed-parameter tractable problems: for any fixed value of k, they are solvable in time bounded by a polynomial of degree α, where α is a constant not dependent on the parameter. In order to deal with parameterized intractability, Downey and Fellows have introduced a hierarchy of classes W[l] ? W[2] ? ? containing likely intractable parameterized problems, and they have shown that such classes have many natural, complete languages. In this paper we analyze several variations of the halting problem for nondeterministic Turing machines with parameterized time, and we show that its parameterized complexity strongly depends on some resources like the number of tapes, head and internal states, and on the size of the alphabet. Notice that classical polynomial-time complexity fails in distinguishing such features. As byproducts, we show that parameterized complexity is a useful tool for the study of the intrinsic power of some computational models, and we underline the different “computational powers” of some levels of the parameterized hierarchy.     

Straightforward α-carbamoylation of NADH-like dihydropyridines and enol ethers

The protonation of NADH-like dihydropyridines and cyclic enol ethers generates reactive cationic intermediates, which interact with isocyanides to afford α-carbamoylated heterocycles after an aqueous quenching, in Ugi and Passerini-type reactions, thus broadening the scope of these multicomponent processes.     

Rapid Quantification of 25-Hydroxyvitamin D<Subscript>3</Subscript> in Human Serum by Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry

LC-MS/MS is widely utilized today for quantification of vitamin D in biological fluids. Mass spectrometric assays for vitamin D require very careful method optimization for precise and interference-free, accurate analyses however. Here, we explore chemical derivatization and matrix-assisted laser desorption/ionization (MALDI) as a rapid alternative for quantitative measurement of 25-hydroxyvitamin D₃ in human serum, and compare it to results from LC-MS/MS. The method implemented an automated imaging step of each MALDI spot, to locate areas of high intensity, avoid sweet spot phenomena, and thus improve precision. There was no statistically significant difference in vitamin D quantification between the MALDI-MS/MS and LC-MS/MS: mean ± standard deviation for MALDI-MS—29.4?±?10.3 ng/mL—versus LC-MS/MS—30.3?±?11.2 ng/mL (P?=?0.128)—for the sum of the 25-hydroxyvitamin D epimers. The MALDI-based assay avoided time-consuming chromatographic separation steps and was thus much faster than the LC-MS/MS assay. It also consumed less sample, required no organic solvents, and was readily automated. In this proof-of-concept study, MALDI-MS readily demonstrated its potential for mass spectrometric quantification of vitamin D compounds in biological fluids.

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Graphical Abstract ?

     

A Sulfoxide‐Based Isobaric Labelling Reagent for Accurate Quantitative Mass Spectrometry

Modern proteomics requires reagents for exact quantification of peptides in complex mixtures. Peptide labelling is most typically achieved with isobaric tags that consist of a balancer and a reporter part that separate in the gas phase. An ingenious distribution of stable isotopes provides multiple reagents with identical molecular weight but a different mass of the reporter groups, allowing relative quantification of multiple samples in one measurement. Here we report a new isobaric labelling reagent, where the balancer and the reporter are linked by a sulfoxide group, which, based on the sulfoxide pyrolysis, leads to easy and asymmetric cleavage at low fragmentation energy. The fragmentation of our new design is significantly improved, yielding more intense complementary ion signals, allowing complementary ion cluster analysis as well.     

The quest for a stable silyne, RSi ≡ CR′. The effect of bulky substituents [1]

The two major fundamental obstacles which so far have prevented theisolation of stable silynes, RSiCR (1), are: (a)the existence of more stable isomers, e.g., RRC=Si: (2) and(b) their extremely facile (exothermic) dimerication. The steric andelectronic effects of various substituents R and R (R = alkoxy,alkyl, aryl and silyl; R = alkyl and aryl groups) on the stability ofRSiCR relative to the isomeric RRC=Si:(E(1-2)), and on the energy of dimerization tothe corresponding 1,3-disilacyclobutadienes (E(D)), werestudied computationally using density functional theory (DFT) and theONIOM method. The goal was to find a combination of substituents thatwill make RSiCR more stable than RRC=Si: and whichwill also prevent its dimerization. For R = R = H,E(1-2)) = 40.7 kcal/mol (i.e., 2 islower in energy than 1), and E(D) = –104.0kcal/mol. 1, R = OH, R = m-Tbt 2,6-bis[bis(silyl)methyl]phenyl, is by 11.1 kcal/mol morestable than the isomeric silylidene 2. However, thedimerization of 1, R = OH, R = m-Tbt remains highlyexothermic (by 101 kcal/mol). 1, R = R = m-Tbt and1, R = (t-Bu)₃Si, R = m-Tbt, are by 5.8 and 2.0kcal/mol, respectively, less stable than the corresponding 2.However, the dimerization of 1, R = (t-Bu)₃Si, = m-Tbt is exothermic by only 12 kcal/mol. For1, R = (t-Bu)₃Si, and R = Tbt 2,6-bis[bis(trimethylsilyl)methyl]phenyl, the corresponding1,3-disilacyclobutadiene dimer 3, dissociates spontaneously.Thus, (t-Bu₃Si)SiCTbt is predicted to be kineticallystable towards both, isomerization to (t-Bu₃Si)TbtC=Si: anddimerization to 3, making it a viable synthetic target. Thereported energies were calculated atB3LYP/6-31G^**//B3LYP/3-21G^*; good agreement is found betweenthe DFT and the ONIOM results.